EP2456546A1

EP2456546A1 - Polyimide membranes made of polymerization solutions

Info

Publication number: EP2456546A1
Application number: EP10734148A
Authority: EP
Inventors: Markus Ungerank; Goetz Baumgarten
Original assignee: Evonik Fibres GmbH
Current assignee: Evonik Fibres GmbH
Priority date: 2009-07-23
Filing date: 2010-07-22
Publication date: 2012-05-30
Anticipated expiration: 2030-07-22
Also published as: BR112012001481B1; KR101896721B1; JP2012533671A; CN102470329B; US10118136B2; CA2769033C; CA2769033A1; US20120123079A1; BR112012001481A2; EP2456546B1; KR20120075454A; HK1169075A1; WO2011009919A1; MY160267A; US20160310912A1; RU2012106081A; RU2566769C2; BR112012001481B8; RU2566769C9; JP6125229B2

Abstract

The invention relates to polyimide membranes and to a phase inversion method for the production thereof. The polyimide membranes can be used to separate different gas mixtures.

Description

Polyimide membranes from polymerization solutions

Field of the invention

The invention relates to polyimide membranes prepared directly from a polyimide polymerization solution without the polyimide being in the form of a solid,

especially not as a dried solid, especially not as a dried powder, isolated and then

was redissolved. The relevant to the invention

Polyimide membranes can be either flat membranes or

Be hollow-fiber membranes. The polyimide membranes can be both pore membranes in the form of micro, ultra or

Nanofiltartionsmembranen be as well as non-porous membranes for the separation of gases. All membranes are integrally asymmetric membranes and are characterized by a

Phase inversion process produced.

task

The object of this invention is to find a manufacturing process for polyimides in which no substances are used which interfere with the subsequent membrane production process. Furthermore, it should be possible with the process according to the invention to produce membranes with sufficient mechanical properties. Other tasks that are not explicitly mentioned emerge from the overall context of the following description, examples and claims.

State of the art

For the preparation of phase inversion membranes, polymers are generally required which are soluble in conventional water-miscible solvents. Thousands of tons are currently being produced by this process

Polyethersulfonmembranen produced. Solvents include but are not limited to

Dimethylformamide (DMF), dimethylacetamide or N-methylpyrrolidone in question. There are many additives such as cosolvents, non-solvents, pore formers,

Hydrophilizing agents and etc. are added to the

To influence the properties of the membranes. This is usually based on a granulate and the

Casting solution prepared by pasting with the solvents and the additives. Decisive for the success in membrane production are also the molecular weight and the distribution of the polymers used. Generally, polymers with high molecular weights and narrow distribution are required.

P84 is a well-known polymer in the literature and is used for the production of flat membranes and

Hollow-fiber membranes used (US 2006/0156920, WO 04050223, US 7018445, US 5635067, EP 1457253, US 7169885, US

20040177753, US 7025804). P84 is available in 2 modifications (P84 type 70 and P84 HT) from HP Polymer in

Lenzing / Austria distributed in powder form. Customers then redissolve this powder in aprotic dipolar solvents and add additives. From this membrane can then be produced. However, several customers (e.g., Air Liquide Medal, US

2006/156920) that the films produced therefrom and Membranes are very brittle and only blends with other polymers lead to stable films and hollow fiber membranes. The powder must be subjected to a special treatment so that it has sufficiently high molar masses. (Air Liquide WO 2006/092677). Here, the duration of treatment and the procedure are very critical. The result are powders with slightly different properties, however

Found casting solutions with different viscosities. Thus, a uniform production of

Polymer membranes difficult.

P84 also works with other polymers in a blend

processed (US 2006/156920), so that from it

produced membranes sufficiently high stabilities

exhibit. The disadvantage here, however, is that the very good separation properties for gases, Plastifizierungsstabilitäten against CO ₂ and chemical stabilities against many solvents are disturbed in part by admixture of other polymers or even destroyed.

The cause of the low molecular weight is in

Manufacturing process of P84 powder. This loses

Polymer at molecular weight. The molecular weights directly after the

Polymerization and after the preparation of the powder are shown in Table 1. TABLE 1 Molar masses after polymerization and after powder production of P84 type 70 and P84 HAT

It can be seen clearly that the polymer loses its molecular weight during the transfer of the polymerization solution into the powder by a precipitation process.

Also for the production of flat membranes P84 powder is used (WO 2007/125367, WO 2000/06293). Here, the same problems apply as in the production of

Hollow fiber membranes. measuring technology

viscosity determination

The dynamic viscosity η is determined by shearing the

Polymer solution in a cylindrical gap at a constant temperature of 25 ° C once by specifying different speeds Ω (or shear rate γ) and then determined by specifying different shear stresses τ.

The measuring instrument used is a HAAKE RS 600 with a temperature-controlled measuring cup holder TEF / Z28, a cylindrical rotor Z25DIN53019 / ISO3219 and an AIu- disposable measuring cup Z25E / D = 28mm

It is the shear stress τ at a certain

Measure shear rate. The dynamic viscosity η is calculated from the following formulas and is measured at a shear rate of 10 s ^-1 in Pa. s specified. τ

Viscosity function - = η * γ '

ϊ

Shear rate γ = M * Ω τ ... shear stress

η ... Dynam. viscosity

M ... Shearing factor of the rotor: 12350 rad / s

Ω ... angular velocity Molar Mass

The molecular weight determination is carried out with the aid of a

Gel permeation chromatography. The calibration is done with polystyrene standards. The reported molecular weights are therefore to be understood as relative molar masses.

The following components and settings were used:

permeabilities

The gas permeabilities are used for films in Barrer (10 -10 , cmHg ^λ ). The permeances of

Hollow fibers or flat membranes for gases are in GPU (Gas Permeation Unit, 10 ^{~. 6} cm ³ 'cm ^{~ 2.} ^{S -1} cmHg ^"1) specified. The Flows of nano and ultrafiltration membranes are given in 1.m ^{~ 2} .h ^"1 .bar ^{" 1} .

gas permeabilities

The measurement of the permeabilities for gases takes place according to the pressure rise method. Here, a flat film with a thickness between 10 and 70 μ is applied to one side with a gas or gas mixture. On the other hand, the permeate side prevails at the beginning of the experiment vacuum (about 10 ^{~ 2} mbar). The pressure increase on the permeate side is now recorded over time.

The permeability of the polymer can be determined according to the following formula: r _ ä Va _ea -MW _ga J dp _{Λ QL0}

pRTAΛp ^' dt ^'

Permeability in Barrer (10 ¹⁰ cm ³ 'cm ² .cm.s ^λ . CmHg ^λ )

Vdead ••• Volume of permeate side in cm ³

MW _gas ... molar mass of the gas in g.mol ^'1

1 ... layer thickness of the film in cm

p .... density of the gas in g.cm ^"3

R ... gas constant in cm ³ . cmHg.K ^"1 .mol ^{" 1}

T ... temperature in Kelvin

A ... surface of the foil in cm ²

Δp ... pressure difference between feed and permeate side in cmHg dp / dt. Pressure increase per time on the permeate side in cmHg. s ^{' 1}

When the permeability of hollow fibers is measured, the same pressure increase method is used. The permeance is calculated according to the following formula:

V _äec , _ä -MW _gas dp _{1 Q6}

pRTAAp ^' dt ^' p ... permeance in GPU (gas permeation units) 10 ⁶ cm ³ 'cm ² .s

¹ ^ mHg ^"1 )

Vdead ••• Volume of permeate side in cm ³

MW _gas ... molecular weight of the gas in g.mol ^"1

p .... density of the gas in g.cm ^"3

R ... gas constant in cm ³ . cmHg.K ^"1 .mol ^{" 1}

T ... temperature in Kelvin

A ... outer surface of the hollow fiber in cm ²

The selectivities of different gas pairs are

Pure gas selectivities. The selectivity between two gases is calculated from the quotient of the permeabilities:

S = ^

S ... ideal gas selectivity

Pi ... permeability or permeance of the gas 1

P2 ... permeability or permeance of the gas 2 Flüssigkeitspermeanzen

The determination of the permeances of flat membranes is carried out with a Milipore stirred cell, with 5 to 6 bar

Nitrogen is applied. The permeate flux per unit of time is measured at a certain pressure. The

Permeanz results from:

P = Ap.A

Permeance in lm ² .h ^x .bar ^λ

v ... volume flow in lh ^"1

Δp ... pressure difference between feed and permeate side in bar A ... Filtration area in m ²

The retention R is given by the following formula:

R = (l - ^ -). 100

R ... retention in%

C _p ... concentration of the solute in the permeate

C _F .... Concentration of the solute in the feed

If the retention is 100%, then the entire fabric is retained by the membrane, the retention is 0%, the membrane passes through the entire solute. the solution of the problem

The problem of molecular weight reduction in the production of the P84 powder is circumvented by using the polymer after the

Polymerization in an aprotic dipolar solvent not in the form of a solid, in particular not as a dried solid, especially not as a dried powder is isolated but the polymerization is used directly for the preparation of the membranes use.

The membrane manufacturing process is as follows

Sub-steps: a) polymerization

b) Preparation of the casting solution

c) membrane production

polymerization

The preparation of the polyimides takes place after a

Polycondensation of an aromatic

Tetracarboxylic anhydrides with an aromatic

Diisocyanate with liberation of carbon dioxide. Described below are the preferred substances used and combinations thereof:

Dianhydrides:

3, 4, 3 '4' - benzophenone tetracarboxylic dianhydride, 1,2,4,5-benzene tetracarboxylic dianhydride, 3, 4, 3 '4' - biphenyl tetratecarboxylic dianhydride, oxydiphthalic,

Sulfonyldiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene diphthaic acid dianhydride

Diisocyanates:

2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-methylene diphenyl diisocyanate, 2,4,6-trimethyl-1,3-phenylene diisocyanate, 2,3,4,5-tetramethyl-1,4-phenylene diisocyanate

The polymerization takes place in an aprotic dipolar solvent. It will be preferable but not

exclusively dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrolidone and sulfolane used individually or in mixtures.

Here, the aromatic dianhydride or mixtures of aromatic dianhydrides in concentrations of 10 wt .-% to 40 wt .-%, preferably between 18 wt .-% and 32% wt .-% and particularly preferably between 22 wt .-% and 28 % Wt .-% dissolved in an aprotic dipolar solvent and heated to 50 ⁰ C to 150 ⁰ C, preferably 70 ⁰ C to 120 ° C and particularly preferably to 80 ⁰ C to 100 ⁰ C. 0.01% by weight to 5% by weight,

preferably from 0.05% to 1% and more preferably from 0.1% to 0.3% by weight of a basic catalyst. As a catalyst come into question: Alkali and alkaline earth hydroxides, methylates, ethanolates, carbonates and phosphates, such as but not limited to sodium hydroxide,

Potassium hydroxide, sodium methylate, potassium methylate,

Sodium ethylate, potassium ethylate, sodium carbonate,

Sodium bicarbonate, potassium carbonate,

Potassium bicarbonate, potassium phosphate,

Potassium hydroxyphosphate, potassium dihydrogen phosphate

• Tertiary amines such as but not

exclusively: trimethylamine, triethylamine,

Tripropylamine, diazabicycloundecane, diazabicyclooctane, dimethylamino pyridine,

The diisocyanate is then added over a period of 1 to 25 hours, preferably 3 to 15 hours and more preferably 5 to 10 hours.

The following polyimides are particularly preferably prepared:

R is selected from the group consisting of

x, y: mole fraction with 0 <x <0.5 and 1> y> 0.5

It creates a clear golden yellow to dark brown

Polymer solution with a viscosity between 1 and 300 Pa. s, preferably 20 to 150 Pa. s, and more preferably 40 to 90 Pa. s. The molecular weights Mp are greater than 100 000 g.mol ^{~ 1} and therefore differ significantly from the

Polyimide polymer, especially the P84 polymer, powders.

The polyimide polymer of the invention is dissolved in an aprotic dipolar solvent after the reaction. There are no interfering impurities or by-products in the polymer solution. The viscosity is very high and

suitable for the production of membranes. For this reason, it is also economically advantageous not to precipitate the polymer and then again in the same solvent

dissolve. The solutions are therefore without isolation of the polymer and preferably without other further

Treatment directly for the production of the casting solution

used. Production of the casting solution

The polymer solutions obtained from the polycondensation have a solids content between 22 wt .-% and 28% wt .-% and can without further treatment for

Production of the casting solution can be used.

The casting solution according to the invention are characterized by the following properties:

• They have a sufficiently high viscosity

Production of flat and hollow fiber membranes

• They may contain additives that prevent the formation of large voids (macrovoids) in the membranes

• You can use volatile solvents for manufacturing

a surface with the desired pore size included

The viscosity of the casting solution is ideal if it corresponds to the so-called "entanglement" point in the course of the viscosity as a function of the solids, which is the point where the dependence of the viscosity on the solid changes from linear to exponential The higher the molecular weight, the lower the solids content at which entanglement occurs. With regard to the viscosity, the molecular weights and the

Molar composition distribution, the casting solutions obtainable by the process according to the invention differ significantly from the casting solutions of the prior art. Only by the process according to the invention casting solutions are available which have a high viscosity in combination with a high molecular weight and a narrow molecular weight distribution of the polyimide. With the invention

Processes can thus be produced membranes which have excellent mechanical properties.

With the prior art methods, i. With

Dissolution of powdered polyimides and subsequent post-treatment to increase the molecular weight can no

Casting solutions are obtained with comparable property combination.

In the process according to the invention can also additives

be added. Various amounts of additives result in different solids contents, which would then shift the Entanglementpunkt. Here, by adjusting the molar mass in the polymerization, this entanglement point can be shifted again.

If the composition of the casting solution moves very far from the concentration at which phase separation takes place, the gradient between solvent and non-solvent in membrane production by phase inversion becomes very large and large voids are obtained in the membranes. These macrovoids also called cavities cause a lower pressure stability of the membranes in the application and limit their use, for example, in use in natural gas purification. You can do the education prevent macrovoids by adding non-solvents. For this purpose, the following water-miscible solvents or mixtures thereof come into question.

The list is only to be seen as a sample list, the experienced connoisseur will find other solvents.

Alcohols such as methanol, ethanol,

Isopropanol, propanol, butanol, butanediol, glycerol,

• Water,

• ketones such as acetone or butanone

In principle, several processes can be used to produce a defined surface of the membrane: In addition to the delayed demixing method, evaporation of volatile cosolvents also leads to very thin selective layers both in the gas separation membrane area and in the nano- and ultrafiltration membrane area. The degree of evaporation and thus the pore size is determined by the type of volatile solvent, its concentration, the

Evaporation time, the temperature of the casting solution, the amount and temperature of the surrounding gas at the Abdampfstrecke influenced.

Suitable volatile solvents are the following solvents. These should be miscible with water, such as acetone, tetrahydrofuran, methanol, ethanol, propanol, isopropanol, dioxane, diethyl ether.

The casting solution is preferably prepared by adding the additives by metering in the mixture of the additives or separately one after the other. there The additives are slowly added to the mixture with stirring. The metered addition is preferably carried out for between 10 minutes and 3 hours, more preferably between 30 minutes and 2 hours. The addition of the cosolvent partially precipitates the polyimide at the point of introduction. The solids dissolve after a few minutes without leaving any residue. The clear solution is then filtered through a 15 μ steel mesh screen to disturbing

To remove any accompanying substances that cause errors in the

Membrane surface would lead.

After filtration, the solution passes through 2 days

Leave at 50 ⁰ C in a closed container of air bubbles and thus degassed.

Production of hollow fibers

The degassed, filtered and mixed with additives

Polyimide polymer solution is preferably thermostated at 20 to 100 ⁰ C, particularly preferably at 30 to 70 ⁰ C. The solution is pumped by a gear pump through the outer part of a two-fluid nozzle. The outer diameter of the two-component nozzle is 600 μm, the inner diameter is 160 μm, the pumping capacity is between 1.3 and 13.5 ml / min. In the inner part of the two-fluid nozzle is a

Liquid mixture of water and one or one

Mixture of several aprotic dipolar solvents pumped.

As a solvent, but not come

exclusively dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, sulfolane or

Dimethyl sulfoxide in question. The composition is between solvent and water is between 10 wt .-% and 95 wt .-%

Solvent and 90% by weight and 5% by weight of water,

preferably between 30% by weight and 90% by weight of solvent and 70% by weight and 10% by weight of water and especially

preferably between 50% by weight and 80% by weight of solvent and 50% by weight and 20% by weight of water. The pumping capacity is between 0.2 ml / min and 10 ml / min.

The resulting hollow fiber now enters a tube, which is flooded with a dry thermostatically controlled gas. Possible gases are: nitrogen, air, argon, helium, carbon dioxide, methane or other technical inert gases. The temperature of the gases is adjusted via a heat exchanger and is preferably between 20 and 250 ⁰ C, more preferably between 30 and 150 ⁰ C and most preferably between 40 and 120 ⁰ C.

The gas velocity in the tube is preferably between 0.1 and 10 m / min, more preferably between 0.5 and 5 m / min and most preferably between 1 and 3 m / min. The distance and thus the length of the tube is preferably between 5 cm and one meter,

more preferably between 10 and 50 cm. The thus conditioned thread then dips into a water bath which coagulates the polymer mass to form the membrane. The temperature of the water bath preferably has between 1 and 60 ⁰ C, particularly preferably 5 to 30 ⁰ C and particularly preferably between 8 and 16 ⁰ C.

The concentration of aprotic dipolar and others

Solvents such as but not limited to dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N- Ethyl pyrrolidone, sulfolane, dimethyl sulphoxide,

Tetrahydrofuran, dioxane, isopropanol, ethanol or glycerol in the precipitation bath is between 0.01 wt .-% and 20 wt .-%, preferably between 0.1 wt .-% and 10 wt .-% and

more preferably between 0.2% and 1% by weight.

The take-off speed of the hollow fibers is between 2 and 100 m / min, preferably between 10 and 50 m / min and particularly preferably between 20 and 40 m / min. The fibers are wound on a spool and washed in water until the residual solvent content is less than 1%. Subsequently, a treatment in ethanol and hexane. The fibers are then preferably between room temperature and 150 ⁰ C, particularly preferably between 50 and 100 ° c dried. This gives fibers with outer diameters of 100 to 1000 .mu.m, preferably between 200 and 700 .mu.m and particularly preferably between 250 and 400 μ.

With the method according to the invention thus obtained

Hollow fiber membranes of polyimides, which show high separation performance for various gases. An excerpt for various polymers and gases is summarized in Table 2.

Table 2: Permeanzen various inventive

Polyimide hollow fibers for single gas measurements

It is also noteworthy that the membranes exhibit hardly any increase in the CO ₂ partial pressures

Permeanz of methane, retain their selectivity and therefore hardly plasticize. This property is necessary for the treatment of acid gases with high CO ₂ contents and high pressures, as is the case, for example, in the processing of raw natural gas or raw biogas. The hollow fiber membranes can also be crosslinked with amines. If the hollow fiber is crosslinked, this is done after the washing step. For this purpose, the hollow fiber is passed through a bath containing an amine

contains at least 2 amino groups per molecule such as e.g. a diamine, triamine, tetraamine or a polyamine. The amine may be primary or secondary, or mixtures of primary, secondary and tertiary amines in one molecule. As amines come aliphatic and

aromatic and mixed aliphatic-aromatic in question. Also amines based on silicone come into question. Examples of aliphatic diamines include but are not limited to: diaminoethane, diaminopropane, diaminobutane, diamniopentane, diaminohexane, diaminoheptane, diaminooctane, diaminodecane or diamino compounds of branched or cyclic aliphatics (eg, cis- and trans -1,4-cyclohexane) and longer chain connections.

However, suitable aromatic compounds are not exclusively: p-phenylenediamines, m-phenylenediamines, 2,4-tolylenediamines, 2,6-tolylenediamines, 4,4'-diaminodiphenyl ethers.

However, suitable examples of mixed aliphatic-aromatic amines include, but are not limited to: aminoalkyl substituted aromatics such as e.g. p-bis (aminomethyl) benzene.

As amines based on silicon, but not exclusively in question: bis (aminoalkyl) siloxanes with different chain length. As representatives of polyfunctional amines, but not exclusively the following compounds are suitable: Oligo- or polyethyleneimines with different

Molar masses (400 to 200,000 g / mol), N, N ', N "trimethyl bis (hexamethylene) triamine, bis (6-aminohexyl) amine

The networking is done by placing in or

continuous pulling of the whole hollow fiber by a solution of the respective diamine in water or a mixture of water and water-miscible solvents or other solvents which do not affect the membrane structure and which dissolve the respective amines. For this purpose, however, are not exclusively in question:

• alcohols, e.g. Methanol, ethanol, isopropanol,

Propanol, butanol, butanediol, glycerin

• ethers such as e.g. Diethyl ether, tetrahydrofuran, dioxane or polyethylene glycols or polyethylene glycol ethers

Aprotic dipolar solvents, e.g.

Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone,

Tetramethylurea, dimethyl sulfoxide or sulfolane

Ketones such as e.g. Acetone or methyl ethyl ketone

• Others such as ethyl acetate, dichloromethane,

Chloroform, toluene, xylene, aliphatics and

Cycloaliphatic compounds such as hexane, heptane or cyclohexane.

The concentration of the diamines is between 0.01 wt .-% and 10 wt .-%, but preferably between 0.05 wt .-% and 5 wt .-% and particularly preferably between 0.1 wt .-% and 1 wt .-%. The temperature of the crosslinking solution is between 1 and 100 ° C, preferably between 10 and 70 ⁰ C and particularly preferably between 20 and 50 ⁰ C.

The residence time is between 10 seconds and 10

Hours, preferably between 1 minute and 60 minutes, and more preferably between 2 and 10 minutes.

To remove the remaining amine, the membrane is washed with water. The Waschbadstemperatur is between 10 and 90 ° C, preferably between 20 and 60 ⁰ C. The dwell time is in the washing bath. 1 to 200 minutes, preferably between 2 and 50 minutes, and more preferably between 3 and 10 minutes.

Hollow fibers obtained in conventional organic solvents such as but not limited to dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetramethylurea, dimethylsulfoxide or sulfolane, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, dioxane, ethyl acetate,

Dichloromethane, chloroform, toluene, xylene, hexane, heptane or cyclohexane are no longer soluble. They can therefore be used in nano-, ultra- and microfiltration in organic solvents. Production of flat membranes

The offset with additives and degassed solution is poured bubble-free in the doctor blade of a Flachmembrangießanlage. The squeegee width can be up to 1.2 m Under the squeegee runs a calendered carrier fleece made of plastic fibers, but preferably not exclusively of polyimide,

Polypropylene, polyamide, polyester or polyphenylene sulfide, at a rate of 0.1 to 10 m / min and

preferably 1 to 5 m / min. The thickness of the nonwoven is between 30 and 300 μ, preferably between 100 and 200 μ. The basis weight is between 20 and 300 g / m ² , preferably between 50 and 150 g / m ² . The gap width between doctor and nonwoven is between 100 and 800 μ, preferably between 200 and 400 μ. The coated web enters a channel which is filled with a gas stream in the

Flooded counterflow. As gases but not only dry air, nitrogen, argon or helium come into question. The gas velocity with which the coated fleece is overflowed here is in the range of 100 to 5,000 m / h, preferably between 200 and 1,000 m / h, the temperatures of the gas can be between 10 and 150 ° C, preferably between 15 and 90 be ^0C. The coated nonwoven then enters a precipitation bath, the

Polymer coagulates and forms the desired membrane. The precipitation bath consists of water or mixtures of water and one or more solvents that are miscible with water. For this purpose are:

• alcohols, e.g. Methanol, ethanol, isopropanol,

Propanol, butanol, butanediol, glycerin

Aprotic dipolar solvents, e.g.

Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone,

Tetramethylurea, dimethyl sulfoxide or sulfolane

Ketones such as e.g. Acetone or methyl ethyl ketone.

The precipitation bath temperature is between 1 and 90 ⁰ C,

preferably between 10 and 50 ⁰ C. After a short

Residence time of 10 s to 10 min, preferably 1 to 5 min, the membrane is wound up in a wet state.

To remove the remaining solvent is the

Membrane washed with water. The Waschbadstemperatur is between 10 and 90 ⁰ C, preferably between 20 and 60 ⁰ C. The dwell time is in the washing bath. 1 to 200 minutes, preferably between 2 and 50 minutes, and more preferably between 3 and 10 minutes.

If the membrane is crosslinked, this is done after the washing step. For this purpose, the membrane is passed through a bath containing an amine having at least 2 amines per molecule such as a diamine, triamine, tetraamine or a polyamine. The amine can be primary or secondary or consist of mixtures of primary, secondary and tertiary amines in one molecule. As amines come aliphatic and aromatic and mixed aliphatic-aromatic in question. Also on amines

Silicone base come into question.

Examples of aliphatic diamines include but are not limited to: diaminoethane,

Diaminopropane, diaminobutane, diamniopentane, diaminohexane, diaminoheptane, diaminooctane, diaminodecane or

Diamino compounds of branched or cyclic

Aliphatic (e.g., cis- and trans -1,4-cyclohexane) and longer chain compounds.

However, suitable examples of mixed aliphatic-aromatic amines include but are not limited to: aminoalkyl-substituted aromatics such as e.g. p-bis (aminomethyl) benzene.

As amines based on silicon, but not exclusively in question: bis (aminoalkyl) siloxanes with different chain length. As a representative of

but not exclusively the following compounds are suitable polyfunctional amines: oligo- or polyethyleneimines having different molecular weights (400 to 200 000 g / mol), N, N ', N "trimethyl bis (hexamethylene) triamine, bis ( 6-aminohexyl) amine

The crosslinking takes place by placing the entire membrane in a solution of the respective diamine in water or a mixture of water and water-miscible solvents or other solvents that do not affect the membrane structure and dissolve the respective amines.

For this purpose, however, are not exclusively in question:

• alcohols, e.g. Methanol, ethanol, isopropanol,

Propanol, butanol, butanediol, glycerin

Aprotic dipolar solvents, e.g.

Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone,

Tetramethylurea, dimethyl sulfoxide or sulfolane

Ketones such as e.g. Acetone or methyl ethyl ketone

• Others such as ethyl acetate, dichloromethane,

Chloroform, toluene, xylene, aliphatics and

Cycloaliphatic compounds such as hexane, heptane or cyclohexane.

The concentration of diamines, the temperature of the

Crosslinking solution, the residence time and the performance of the washing step correspond to the values or procedures given above for the crosslinking of the hollow fibers.

After the washing or cross-linking operations, the membrane is impregnated to preserve the pores in the

to ensure subsequent drying process. This is done by immersing the membrane in a mixture of water and a water-miscible high boiler.

Here come for example but not exclusively in

Question: Glycerol, polyethylene glycols of various kinds

Chain length in mixture or individually, Polyethylene glycol dialkyl ethers of various chain lengths in mixture or individually as methyl or ethyl ether, mono- or diols having a boiling point above 200 ⁰ C such as decanol, 1, 4-butanediol, 1, 6-hexanediol.

The concentration of the high boilers in the water is between 5% and 95%, but preferably between 25% by weight and 75% by weight. The temperature of the impregnating solution is

between 1 and 100 ^° C., preferably between 10 and 70 ^° C., and more preferably between 20 and 50 ^° C.

The residence time is between 10 seconds and 10

After impregnation, the drying of the membrane takes place. The drying can be carried out in ambient air or continuously in a convection dryer. The temperature of the drying is in the range of 20 to 200 ^° C.,

preferably between 50 and 120 ^° C. The drying time is between 10 seconds and 10 hours, preferably between 1 minute and 60 minutes, and particularly preferably

between 2 and 10 min. After drying, the finished membrane is wound up and can continue to

Spiral winding elements or bag modules are processed.

The flat and hollow fiber membranes according to the invention

Thus, they are characterized in that they comprise a polyimide which has a Mp> 100,000 g.mol ^-1 , preferably 110,000 to 200,000 g.mol ^-1 , particularly preferably 120,000 to 170,000 g.mol ^-1 and a PDI in the range of 1.7 to 2.3, preferably 1.8 to 2.1. Mp corresponds to the Peak maximum of the molecular weight distribution when calibrated against polystyrene standards in 0.01 mol / l lithium bromide in dimethylformamide.

The high molecular weight causes an improvement in the

mechanical properties in terms of strength and toughness of the membranes. This is especially necessary at high pressures in the applications. Thus, the flat membranes must withstand operation at least 40 bar, certain hollow fiber membranes in the natural gas treatment over 100 bar.

A high molecular weight is also advantageous in order to set a sufficiently high viscosity even at moderate solids contents. The casting solutions need a certain amount

Viscosity to be stable to membranes and hollow fibers

can be processed and that so dense and selective layers can be made on the surface.

Preparation Examples

The following examples serve to illustrate and to better understand the present invention, but do not restrict it in any way.

Preparation of polyimide solutions

Example 1: Preparation of a polyimide solution P84 type 70 in dimethylacetamide

In a 3 1 glass reactor equipped with stirrer and reflux condenser 1622 g of dimethylacetamide are presented anhydrous. 456.4 g 3, 3 ', 4,4'-

Benzophenontetracarbonsäuredianhydrid dissolved and heated to 90 ⁰ C. To this solution is added 0.45 g of sodium hydroxide. Under nitrogen, 266.8 g of a mixture of 64% 2,4-tolylene diisocyanate, 16% 2,6-tolylene diisocyanate and 20% of 4,4'-diisocyanatodiphenylmethane are metered in over several hours. CO2 escapes as a by-product and a polyimide in solution is formed directly.

This gives a golden-colored highly viscous solution having a solids content of 25% and a viscosity of 49 Pa. s ..

The determination of the molar masses by means of

Gel permeation chromatography gives the following values: Mn = 80,600 g.mol ^"1 , Mp = 139600 g.mol ^{" 1} , Mw = 170000 g.mol ^"1 PDI = 2.11 Example 2: Preparation of a polyimide solution P84 type 70 in dimethylformamide

In a 3 1 glass reactor equipped with stirrer and reflux condenser 1622 g of dimethylformamide are presented anhydrous. 456.4 g 3, 3 ', 4,4'-

This gives a golden colored highly viscous solution having a solids content of 27% and a viscosity of 48 Pa. s .. The determination of molecular weights by means of

Gel permeation chromatography gives the following values: Mn = 76 600 g. mol ^"1 , Mp = 130500 g.mol ^{" 1} , Mw = 146200 g.mol ^"1 PDI = 1.91

Example 3: Preparation of a polyimide solution P84 type 70 in N-methylpyrrolidone

In a 3 1 glass reactor equipped with stirrer and reflux condenser 1800 g of N-methylpyrrolidone anhydrous are presented. 456.4 g 3, 3 ', 4,4'-

Benzophenontetracarbonsäuredianhydrid dissolved and heated to 90 ⁰ C. To this solution is added 0.45 g of sodium hydroxide. Under nitrogen, 266.8 g of a mixture of 64% 2,4-tolylene diisocyanate, 16% 2,6- Tolylene diisocyanate and 20% 4, 4 '-diisocyanatodiphenylmethane added during several hours. CO2 escapes as a by-product and a polyimide in solution is formed directly.

This gives a golden colored highly viscous solution having a solids content of 25% and a viscosity of 45 Pa. s .. The determination of molecular weights by means of

Gel permeation chromatography gives the following values:

Mn = 65700 g.mol ^"1 , Mp = 107200 g.mol ^{" 1} , Mw = 147000 g.mol ^"1 PDI = 2.24

Example 4: Preparation of a polyimide solution P84 type 70 in N-ethylpyrrolidone

In a 3 1 glass reactor equipped with stirrer and reflux condenser 1622 g of N-ethylpyrrolidone anhydrous are presented. 456.4 g 3, 3 ', 4,4'-

This gives a golden-colored highly viscous solution having a solids content of 27% and a viscosity of 87 Pa. s .. The determination of molecular weights by means of

Gel permeation chromatography gives the following values: Mn = 64,600 g. mol ^"1 , Mp = 105200 g.mol ^{" 1} , Mw = 144700 g.mol ^"1 PDI = 2.24 Example 5: Preparation of a polyimide solution P84 T100 in dimethylformamide

In a 3 1 glass reactor equipped with stirrer and reflux condenser 1800 g of dimethylformamide are presented anhydrous. 473.6 g 3, 3 ', 4,4'-

Benzophenontetracarbonsäuredianhydrid dissolved and heated to 90 ⁰ C. To this solution is added 1.8 g of diazabicyclooctane. Under nitrogen, 254.4 g of 2,4-tolylene diisocyanate are metered in over several hours.

CO2 escapes as a by-product and a polyimide in solution is formed directly.

This gives a golden colored highly viscous solution having a solids content of 25% and a viscosity of 59 Pa. s .. The determination of molecular weights by means of

Gel permeation chromatography gives the following values: Mn = 82 100 g.mol ^"1 , Mp = 151 500 g.mol ^{" 1} , Mw = 181 900 g.mol ^"1 PDI = 2.21

Example 6: Preparation of a polyimide solution P84 T80 in dimethylformamide

In a 3 1 glass reactor equipped with stirrer and reflux condenser 1622 g of dimethylformamide are presented anhydrous. 473.6 g 3, 3 ', 4,4'-

Benzophenontetracarbonsäuredianhydrid dissolved and heated to 90 ⁰ C. To this solution is added 1.8 g of diazabicyclooctane. Under nitrogen, 254.4 g of a mixture of 80% 2, 4-tolylene diisocyanate and 20% 2,6-Tolylendiisocynat be metered in over several hours. there CO2 escapes as a by-product and a polyimide in solution is formed directly.

This gives a golden colored highly viscous solution having a solids content of 27% and a viscosity of 108 Pa. s .. The determination of molecular weights by means of

Gel permeation chromatography gives the following values: Mn = 83,800 g.mol ^"1 , Mp = 152,300 g.mol ^{" 1} , Mw = 173,800 g.mol ^"1 PDI = 2.07

Example 7: Preparation of a polyimide solution P84 HT in dimethylformamide

In a 3 1 glass reactor equipped with stirrer and reflux condenser 1800 g of dimethylformamide are presented anhydrous. Therein are 316.4 g of 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 142.8 g

Pyromellitic dianhydride dissolved and heated to 90 ⁰ C. To this solution is added 1.8 g of diazabicyclooctane. Under nitrogen, 283.4 g of a

Mixture of 80% 2, 4-tolylene diisocyanate and 20% 2,6-Tolylendiisocynat dosed for several hours. CO2 escapes as a by-product and a polyimide in solution is formed directly.

This gives a golden-colored highly viscous solution having a solids content of 27% and a viscosity of 70 Pa. s .. The determination of molecular weights by means of

Gel permeation chromatography gives the following values: Mn = 75,500 g.mol ^"1 , Mp = 122,200 g.mol ^{" 1} , Mw = 150,900 g.mol ^"1 PDI = 2.00 Example 8: Preparation of a polyimide solution P84 MDI in dimethylformamide

In a 3 1 glass reactor equipped with stirrer and reflux condenser, 1500 g of dimethylformamide anhydrous presented. It contains 369.2 g of 3, 3 ', 4,4'-

Benzophenontetracarbonsäuredianhydrid dissolved and heated to 90 ⁰ C. To this solution is added 1.5 g of diazabicyclooctane. Under nitrogen, 222.3 g of 2, 4, 6-trimethyl-l, 3-phenylene diisocyanate are metered in over several hours. CO2 escapes as a by-product and a polyimide in solution is formed directly.

This gives a pale yellow viscous solution with a

Solids content of 25% and a viscosity of 5 Pa. s .. The determination of molecular weights by means of

Gel permeation chromatography gives the following values: Mn = 55 200 g.mol ^"1 , Mp = 95,000 g.mol ^{" 1} , Mw = 112,000 g.mol ^"1 PDI = 2,03

Film production and intrinsic gas permeabilities

The polymerization solutions are filtered undiluted through a 15 μ metal screen. To produce the films, a device from Elcometer (Elcometer 4340) is used with a squeegee. There are glass plates with the help of a squeegee and a

Gap of 250 μ coated with the polymer solutions. The solvent is ⁰ to 250 C (12h) following evaporated in a circulating air drying cabinet at 70 ⁰ C (0.5 h), 150 ° C (2 h). The films are then virtually free of solvents (content <0.1%) and are released from the glass plates. This gives films with a thickness of about 30 to 40 microns. None of the films were brittle, all showed good mechanical

Properties. From these slides are then using

Microscope searched for error-free locations and cut round samples with a diameter of 46 mm. These are then placed in the home-made Gaspermeationsapparatur and determines the permeability of various gases by the vacuum method.

Here, the films are coated with a single gas (e.g.

Nitrogen, oxygen, methane or carbon dioxide) at different pressures and the increase in pressure on the permeate side recorded. From this the permeability is calculated in Barrer (10-6 cm ³ .cm ^"2 .s ^{" 1} .cmHg ^"1 ) Below are some examples given.

Example 9: Gas permeabilities of the various polymers from the above examples

Additization of the polymerization solution

Example 10 Production of a casting solution of P84 Type 70 for the production of polyimide hollow fibers

In a 3 1 stirred tank made of glass with a strong stirrer at room temperature 1168 g P84 type 70 solution in

Dimethylformamide from Example 2 was added dropwise with a mixture of 94.1 g of tetrahydrofuran and 40.3 g of isopropanol. The polymer precipitates briefly at the point of dropping, but dissolves again immediately. It is stirred until a homogeneous solution is formed. This is then filtered through a sieve with a mesh size of 15μ and allowed to stand for 2 days without stirring. You get one

Casting solution having a solids content of 23.5%, a dimethylformamide content of 66.5%, a

Tetrahydrofuran content of 7% and an isopropanol content of 3%

Example 11: Preparation of a casting solution of P84 type 70 for the production of polyimide hollow fibers

In a 3 1 glass stirred tank with strong stirrer at room temperature 1034 g P84 type 70 solution in

Dimethylformamide from Example 2 was added dropwise with a mixture of 58.6 g of tetrahydrofuran and 46.9 g of isopropanol. The polymer precipitates briefly at the point of dropping, but dissolves again immediately. It is stirred until a homogeneous solution is formed. This is then filtered through a sieve with a mesh size of 15μ and 2 days left without stirring. This gives a casting solution having a solids content of 23.8%, a dimethylformamide content of 67.2%, a

Tetrahydrofuran content of 5% and an isopropanol content of 4%

Example 12 Production of a Casting Solution from P84 HT for the Production of Polyimide Hollow Fibers

In a 3 1 glass stirred tank with strong stirrer at room temperature 1034 g P84 HT solution in

Dimethylformamide from Example 7 added dropwise with a mixture of 47 g of tetrahydrofuran and 65 g of isopropanol. The polymer precipitates briefly at the point of dropping, but dissolves again immediately. It is stirred until a homogeneous solution is formed. This is then filtered through a sieve with a mesh size of 15μ and allowed to stand for 2 days without stirring. You get one

Casting solution having a solids content of 23.6%, a dimethylformamide content of 66, 9%, a

Tetrahydrofuran content of 4% and an isopropanol content of 5, 5%

Example 13: Preparation of a pouring solution of P84 T100 for the production of polyimide hollow fibers

In a 3 1 glass stirred tank with strong stirrer at room temperature 1034 g P84 TlOO solution in

Dimethylformamide from Example 5 is added dropwise with a mixture of 46.8 g of tetrahydrofuran and 58.5 g of isopropanol. The polymer precipitates briefly at the point of dropping, but dissolves again immediately. It is stirred until a homogeneous solution is formed. This is then filtered through a sieve with a mesh size of 15μ and allowed to stand for 2 days without stirring. You get one

Casting solution having a solids content of 22.1%, a dimethylformamide content of 68.9%, a Tetrahydrofuran content of 5% and an isopropanol content of 4%

Example 14: Preparation of a pouring solution of P84 type 70 for the production of flat membranes for organophilic nanofiltration

Dimethylformamide from Example 2 added dropwise with 258.5 g of tetrahydrofuran. It is stirred until a homogeneous solution is formed. This is then filtered through a sieve with a mesh size of 15μ and allowed to stand for 2 days without stirring. This gives a casting solution with a

Solids content of 21.6%, a dimethylformamide content of 58.4% and a tetrahydrofuran content of 20%

Hollow fiber production

Example 15 Hollow fiber production from a casting solution with P84 type 70 in dimethylformamide from Example 10

The degassed, filtered and mixed with additives solution of P84 type 70 in dimethylformamide from Example 10 is thermostated at 50 ⁰ C and promoted by a gear pump through a two-fluid nozzle. The flow is 162 g / h. While the polymer solution is conveyed outside the two-substance nozzle, a mixture of 70% is inside Promoted dimethylformamide and 30% water to produce the hole of the hollow fiber. The flow is 58 ml / h. After a distance of 40 cm, the hollow fiber enters 10 ⁰ C cold water. Here, the hollow fiber is wrapped with a tube. This tube is flooded with a nitrogen flow of 2 l / min, the tube internal temperature is 41 ^° C. The fiber is then drawn through a water-washing bath and finally at a speed of 15 m / min

wound. After extraction with water for several hours, the hollow fibers are first dipped in ethanol and then in heptane and then dried in air. This gives hollow fibers with an outer diameter of 412 μ, a hole diameter of 250 μ and a wall thickness of 81 μ.

Single gas measurements yield the following permeances of

Hollow fibers at a transmembrane pressure of 5 bar:

Oxygen: 1,450 GPU

Nitrogen: 0.165 GPU

Carbon dioxide: 6.03 GPU

Methane: 0.084 GPU

The Einzelgasselektivitäten thus be between

Oxygen and nitrogen 8,8 and between carbon dioxide and

Methane 71.9

Single gas measurements yield the following permeances of

Hollow fibers at a transmembrane pressure of 40 bar:

Carbon dioxide: 8.99 GPU

Methane: 0.101 GPU

The individual gas selectivities are between carbon dioxide and methane 88.5 Example 16: Hollow fiber production from a casting solution with P84 type 70 in dimethylformamide from example 11

The degassed, filtered and mixed with additives solution of P84 type 70 in dimethylformamide from Example 11 is thermostated at 50 ⁰ C and promoted by a gear pump through a two-fluid nozzle. The flow is 162 g / h. While outside of the two-fluid nozzle the

Polymer solution is promoted inside a mixture of 70% dimethylformamide and 30% water to produce the hole of the hollow fiber. The flow is 58 ml / h. After a distance of 42 cm, the hollow fiber enters 10 ⁰ C cold water. Here, the hollow fiber is wrapped with a tube. This tube is flooded with a nitrogen flow of 2 l / min, the tube internal temperature is 46 ° C. The fiber is then drawn through a water-washing bath and finally wound up at a speed of 24 m / min. After extraction with water for several hours, the hollow fibers are first dipped in ethanol and then in heptane and then dried in air. This gives hollow fibers with an outer diameter of 310 μ, a hole diameter of 188 μ and a wall thickness of 61 μ.

Single gas measurements yield the following permeances of

Hollow fibers at a transmembrane pressure of 9 bar:

Oxygen: 1.463 GPU

Nitrogen: 0.164 GPU

The Einzelgasselektivitäten thus be between

Oxygen and nitrogen 8,9 Example 17 Hollow fiber production from a casting solution with P84 T100 in dimethylformamide from Example 13

The degassed, filtered and mixed with additives solution of P84 TlOO in dimethylformamide from Example 13 is thermostated at 50 ⁰ C and promoted by a gear pump through a two-fluid nozzle. The flow is 162 g / h. While the polymer solution is conveyed outside the two-substance nozzle, a mixture of 70% is inside

Promoted dimethylformamide and 30% water to produce the hole of the hollow fiber. The flow is 58 ml / h. After a distance of 42 cm, the hollow fiber enters 10 ⁰ C cold water. Here, the hollow fiber is wrapped with a tube. This tube is flooded with a nitrogen flow of 2 l / min, the tube internal temperature is 46 ° C. The fiber is then drawn through a water-washing bath and finally at a speed of 20 m / min

wound. After extraction with water for several hours, the hollow fibers are first dipped in ethanol and then in heptane and then dried in air. This gives hollow fibers with an outer diameter of 339 μ, a hole diameter of 189 μ and a wall thickness of 75 μ.

Single gas measurements yield the following permeances of

Hollow fibers at a transmembrane pressure of 9 bar:

Oxygen: 0.564 GPU

Nitrogen: 0.072GPU

Carbon dioxide: 1, 679

Methane: 0.023 The Einzelgasselektivitäten thus be between

Oxygen and nitrogen 7,8 and between carbon dioxide and methane 71,6

Example 18: Hollow fiber production from a casting solution with P84 HT in dimethylformamide

The degassed, filtered and admixed with additives solution of P84 HT in dimethylformamide from Example 12 is thermostated at 50 ° C and conveyed by a gear pump through a two-fluid nozzle. The flow is 162 g / h. While the polymer solution is conveyed outside the two-substance nozzle, a mixture of 70% is inside

Promoted dimethylformamide and 30% water to produce the hole of the hollow fiber. The flow is 58 ml / h. After a distance of 15 cm, the hollow fiber enters 10 ⁰ C cold water. Here, the hollow fiber is wrapped with a tube. This tube is flooded with a nitrogen flow of 1 l / min, the tube internal temperature is 40 ^° C. The fiber is then drawn through a water-washing bath and finally at a speed of 24 m / min

wound. After extraction with water for several hours, the hollow fibers are first dipped in ethanol and then in heptane and then dried in air. This gives hollow fibers with an outer diameter of 306 μ, a hole diameter of 180 μ and a wall thickness of 63 μ.

Single gas measurements yield the following permeances of

Hollow fibers at a transmembrane pressure of 10 bar:

Carbon dioxide: 6.0 GPU

Methane: 0.2 GPU The Einzelgasselektivitäten thus be between

Carbon dioxide and methane 30

Example 19: Hollow fiber production from a

Polymerization solution of P84 HT in dimethylformamide from Example 7

The degassed and filtered solution of P84 HT in

Dimethylformamide from Example 7 is at 50 ⁰ C.

thermostated and conveyed by a gear pump through a two-fluid nozzle. The flow is 162 g / h. While outside of the two-fluid nozzle, the polymer solution

will be promoted inside a mix of 70%

Promoted dimethylformamide and 30% water to produce the hole of the hollow fiber. The flow is 58 ml / h. After a distance of 15 cm, the hollow fiber enters 10 ⁰ C cold water. Here, the hollow fiber is wrapped with a tube. This tube is flooded with a nitrogen flow of 1 l / min, the tube internal temperature is 70 ⁰ C. The fiber is then drawn through a water-washing bath and finally at a speed of 24 m / min

wound. After extraction with water for several hours, the hollow fibers are first dipped in ethanol and then in heptane and then dried in air. This gives hollow fibers with an outer diameter of 307 μ, a hole diameter of 189 μ and a wall thickness of 59 μ.

Single gas measurements yield the following permeances of

Hollow fibers at a transmembrane pressure of 10 bar:

Carbon Dioxide: 3.37 GPU

Methane: 0.051 GPU The Einzelgasselektivitäten thus be between

Carbon dioxide and methane 66.

The fiber was measured at higher pressures in order to measure the plasticizing behavior and the pressure stability.

Flat membrane production

Example 20: Production of a flat membrane made of P84 type 70

On a flat membrane plant from a casting solution described in Example 14 35 cm wide membranes

produced. The casting solution is calendered by means of a doctor blade and a pouring gap of 200 μ

Polyester fleece with a basis weight of 100 g / m2 and a speed of 5 m / min coated. The coated polyester fleece is then passed through a shaft through which nitrogen flows. The

Flow rate is 339 m / h. The residence time thus achieved is 3 s. The coated nonwoven then dipped in 10 ⁰ C cold water. The raw membrane is then wound up wet.

Subsequently, the membrane is extracted at 70 ^° C. in water and treated with a conditioner (25%).

Polyethylene glycol dimethyl ether (PGDME 250 of the company

Clariant) in water). Drying takes place in a floating dryer at a temperature of 60 ^° C.

The membrane is characterized in a Milipor stirred cell at a pressure of 5 bar. The solvent used is heptane, in which hexaphenylbenzene is in one

Concentration of 12 mg / 1 dissolved. The measurement showed a flux of 1.7 1.m ^{~ 2} .h ^"1 .bar ^{" 1} with a retention of 94%.

The membrane is then also tested at a pressure of 30 bar and 30 ⁰ C in toluene. The test molecules used are oligostyrenes. The river in this test of

Toluene is 90 1. m ^"2 ^ ^{" 1} . The membrane shows very high retention over the entire molecular weight range and a sharp cut-off in the range between 200 and 300 daltons (see Figure 3). Crosslinking of the membranes with diamines

Example 21: Crosslinking of a flat membrane with amines

The flat membrane from Example 20 was for 16 h in a 0.1% ethanolic solution of a Oligoethylenimines

(# 468533, Aldrich, Typical molecular weight 423, contains 5-20% tetraethylenepentamine) The membrane cross-links and shows no solubility in hexane, heptane, toluene, xylene, acetone, butanone, methanol, ethanol,

Isopropanol, tetrahydrofuran, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and ethyl acetate.

The membrane is characterized in a Milipor stirred cell at a pressure of 5 bar. The solvent used is dimethylformamide in which hexaphenylbenzene is dissolved in a concentration of 2.2 mg / l. The measurement showed a flux of 1.3 1.m ^{~ 2} .h ^"1 .bar ^{" 1} with a retention of 89%.

Example 22: Crosslinking of a hollow-fiber membrane with amines

The hollow-fiber membrane from Example 19 was placed in a 0.1% strength solution of hexamethylenediamine in ethanol for 16 hours. The membrane crosslinks and shows no solubility in hexane, heptane, toluene, xylene, acetone, butanone, methanol, ethanol, isopropanol, tetrahydrofuran, dichloromethane, chloroform, Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and ethyl acetate.

figure description

Figure 1: Influence of the concentration of P84 type 70 in DMF on the viscosity of the solution: Comparison of a P84 polymerization solution and a P84 solution prepared from a precipitated and redissolved polymer at 25 ° C.

Figure 2: Cross sections of hollow fiber membranes with

(left image) and without (right image) macrovoids

Figure 3:

Application test of the membrane from Example 20.

Claims

claims

1) Process for producing polyimide membranes,

characterized in that

it's the steps

a) Preparation of the polyimide

b) Preparation of a casting solution comprising the

polyimide

c) Preparation of a polyimide membrane from the

casting solution

includes,

that the polyimide between the steps a) and b) not in the form of a solid, especially not as a dried solid, especially not as

dried powder, isolated and redissolved,

and

that the manufacture of the membrane by a

Phase inversion process takes place.

Method according to claims 1,

characterized in that

for the preparation of the polyimides in stage a)

aromatic dianhydrides or mixtures thereof, preferably 3, 4, 3 ', 4'

Benzophenontetarcarbonsäuredianhydrid,

Pyromellitic dianhydride, 3, 4, 3 ', 4' - biphenyltetracarboxylic dianhydride

and or

aromatic diisocyanates or mixtures thereof, preferably 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-methylene diphenyl diisocyanate, 2,4,6-trimethyl-1,3-phenylene diisocyanate, 2,3,5,6-tetramethyl- 1, 4-phenylene diisocyanate

and or

aprotic dipolar solvents or mixtures thereof, preferably dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, N-ethylpyrrolidinone, sulfolane, tetrahydrofuran, dioxane

be used.

Method according to one of claims 1 or 2,

characterized in that

when the polyimide is a polyimide having the structure:

R is selected from the group consisting of

x, y: mole fraction with 0 <x <0.5 and 1> y> 0.5

4) Method according to one of claims 1 to 3,

characterized in that

for the preparation of the casting solution in step b)

water-soluble additives are added, with preference as additives

volatile water-miscible solvents such as diethyl ether, tetrahydrofuran, dioxane or acetone or mixtures thereof

and or

Non-solvents such as water, methanol, ethanol, n-propanol, isopropanol, butanol, butanediol, Ethylene glycol, glycerol, gamma-butyrolactone or mixtures thereof

and or

Pore former, preferably polyvinylpyrolidinone and / or

water-miscible solvents such as

Dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, N-ethylpyrrolidinone, sulfolane, dimethyl sulfoxide or mixtures thereof

be used.

Method according to one of claims 1 to 4,

characterized in that

in step c) a carrier fleece with a

Polyimidgießlösung is coated, wherein preferably after the coating of the carrier web with a Polymergießlösung a portion of the solvent with a dry thermostated nitrogen or air stream is evaporated to adjust the separation limits of the membrane

Method according to one of claims 1 to 5,

characterized in that

the polyimide membranes with aliphatic diamines or

Polyethyleneimines is crosslinked, with preference

aliphatic diamines diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane,

Diaminooctane, diaminodecane, diaminododecane, bis-4,4'- (aminomethyl) benzene, oligoethyleneimines, Polyethyleneimines or mixtures thereof can be used

and or

the crosslinking is carried out by immersion in a solution of diamine in water or alcohols such as methanol or ethanol or isopropanol or mixtures thereof

and or

the crosslinking takes place at temperatures between 0 and 90 ^° C., preferably between 10 and 60 ^° C., and particularly preferably between 15 and 30 ^° C.

and or

the crosslinking time is between 10 seconds and 16 hours, preferably between 30 seconds and 30 minutes, and more preferably between 1 and 5 minutes

and or

the concentration of the diamine is between 0.01% by weight and 50% by weight, preferably between 0.1% by weight and 10% by weight and more preferably between 0.2% by weight and 1% by weight. % lies.

7) Method according to one of claims 1 to 4,

characterized in that

in step c) an integrally asymmetric

Hollow fiber membrane is produced, wherein preferably the hollow fiber by means of a two-fluid nozzle of a

Polyimide casting solution according to claim 4 and a Bore solution spun in a continuous process becomes .

Method according to claim 7,

characterized in that

Boron solution may be a mixture of water or alcohols with dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, N-ethylpyrrolidinone, sulfolane, dimethylsulfoxide or combinations thereof

and or

that the spinneret has a distance of 1 to 60 cm from a spinning bath of water into which the

Hollow fiber is spun and formed by precipitation of the polymer an integrally asymmetric hollow fiber membrane

and or

that during the spinning process of the hollow thread before the

Entry into the spin bath with a dry

thermostated nitrogen or air stream is circulated to the separation properties of the membrane

adjust

and or

that the polyimide polymer with aliphatic

Diamines or polyethyleneimines crosslinked, with particular preference

as aliphatic diamines diaminoethane,

Diaminopropane, diaminobutane, diaminopentane,

Diaminohexane, diaminooctane, diaminodecane,

Diaminododecane, bis-4,4 '- (aminomethyl) benzene, oligoethyleneimine or polyethyleneimine or mixtures thereof

and or

polyimide

characterized in that

it comprises a polyimide having an Mp> 100,000 g.mol ^'1 (Mp = peak maximum of the molecular weight distribution,

Calibration against polystyrene standards in 0.01 mol / 1

Lithium bromide in dimethylformamide) and a PDI in the

Range of 1.7 to 2.3, preferably 1.8 to 2.1

having . 10: polyimide membrane according to claim 9,

characterized in that

the polymide is a polyimide having the following structure:

R is selected from the group consisting of

x, y: mole fraction with 0 <x <0.5 and 1> y> 0.5

11) polyimide membranes according to claim 9 or 10,

characterized in that

it is micro, ultra or

Nanofiltration membranes are those that can be used to separate homogeneously dissolved or particulate matter from organic solvents or from water or that are membranes without pores, which can be used for the separation of gases. 12) Polyimide membranes according to one of claims 9 to 11, characterized in that

it is in the polyimide membranes to

integrally asymmetric flat membranes on a carrier fleece, preferably a carrier fleece

Polyphenylene sulfide, polyethylene terephthalate or

polypropylene,

or integrally asymmetric hollow fiber membranes.

13) polyimide hollow fiber membranes according to claim 12,

characterized in that

they are preferred for the separation of various gas mixtures

for the separation of methane and carbon dioxide and / or

for the separation of oxygen and nitrogen and / or

for the separation of hydrogen from process gases and / or

for the separation of water vapor from gases or gas mixtures

various kinds

can be used.

14) A polyimide membrane according to any one of claims 9 to 13 and obtainable according to any one of claims 1 to 8. 15) casting solution, obtainable according to one of claims 1 to 4.